Aqueous herbicidal concentrate comprising a betaine type surfactant

ABSTRACT

The present invention concerns an aqueous phytopathological formulation comprising a hydrosoluble salt of at least one aminophosphate or aminophosphonate type herbicide; at least one principal surfactant selected from alkylbetaines and alkyl(amidoalkyl)betaines, and at least one additive selected from at least one of the following compounds:
         (i) amines or etheramines comprising at least one hydrocarbon radical containing 2 to 24 carbon atoms, optionally polyalkoxylated;   (ii) acid or non acid phosphate mono- or di-esters, optionally polyalkoxylated;   (iii) alkali metal, alkaline-earth metal, ammonium, alkylammonium, alkanolammonium, iron, zinc or manganese salts of a mineral acid; and   (iv) alkylmonoglycosides or alkylpolyglycosides.

This application is an application under 35 U.S.C. Section 371 ofInternational Application Number PCT/EPO3/00825 filed on Jan. 28, 2003.

The present invention relates to aqueous phytopathological formulationscomprising at least one aminophosphate or aminophosphonate typeherbicide and at least one betaine type principal surfactant associatedwith one or more particular additives.

Among the various normal presentations of phytopathological formulationsthat can be cited are concentrated aqueous formulations which arediluted by the user prior to applying them to the plants to be treated.

In addition to the active ingredient or ingredients, such aqueousformulations comprise additives known as biological activators the roleof which is to increase the efficacy of the herbicide, for example byencouraging wetting of the plant by that active ingredient or byencouraging penetration into the plant.

Particularly regarding aqueous commercial formulations comprising activeingredients of the amino acid type cited above, one of the mostfrequently used biological activators is an ethoxylated amine.

The presence of these amines considerably strengthens the biologicalactivity of the herbicide, most probably by activating diffusion of theherbicide through the cuticular barrier of the plant.

The major disadvantage with ethoxylated amine compounds is theirchemical toxicity. They are irritants and are only slightlybiodegradable. Further, they are highly ecotoxic, more particularlytowards aquatic plant organisms (algae) or aquatic animals (insects,batrachia) even at low concentrations.

The ever more serious view taken of these different problems has led toa search for phytopathological compounds, preferably hydrosolublephytopathological compounds, with a biological activity that iscomparable to current formulations and with substantially reducedtoxicity and ecotoxicity.

Thus, the present invention aims to provide novel aqueousphytopathological formulations comprising at least one activeingredient, more particular a herbicide of the aminophosphate oraminophosphonate type, with a proportion of ethoxylated amine withrespect to the herbicide that is lower than in the normal formulations,or even free of such amines, while retaining an activity that is atleast equal to said formulations.

These and other aims are accomplished by the present invention whichthus concerns aqueous phytopathological formulations comprising ahydrosoluble salt of at least one aminophosphate or aminophosphonatetype herbicide; at least one principal surfactant selected fromalkylbetaines and alkyl(amidoalkyl)betaines, and at least one additiveselected from at least one of the following compounds:

-   (i) amines or etheramines comprising at least one hydrocarbon    radical containing 2 to 24 carbon atoms, optionally polyalkoxylated;-   (ii) acid or non acid phosphate mono- or di-esters, optionally    polyalkoxylated;-   (iii) alkali metal, alkaline-earth metal, ammonium, alkylammonium,    alkanolammonium, iron, zinc or manganese salts of a mineral acid;    and-   (iv) alkylmonoglycosides or alkylpolyglycosides.

The particular choice of principal surfactant combined with at least oneof the additives listed above can produce phytopathological formulationswith a reduced ethoxylated amine content, or even formulations that arefree of this type of compound while retaining a level of efficacy thatis at least as good as that achieved with commercially availableformulations.

The consequences of this reduction in the amount of ethoxylated amineare to be found in the significant reduction in the toxicity of thefinal formulation itself. These characteristics are still furtherimproved when the formulation is free of that amine.

Further, the formulation of the invention is stable on storage and doesnot cause problems during use. No gel appears, nor does the viscosityincrease greatly during dilution prior to application.

Other advantages and characteristics of the present invention willbecome apparent from the following description and examples.

As indicated above, the formulation of the invention comprises, as anactive ingredient, a hydrosoluble salt of at least one herbicide of theaminophosphate or aminophosphonate type.

Preferably, the formulations of the invention comprise at least onehydrosoluble salt of N-phosphonomethyl glycine.

The term “glyphosate” will be used below to define hydrosoluble salts ofN-phosphonomethyl glycine.

Suitable salts that can more particularly be cited are the salts ofalkali metals such as sodium or potassium; ammonium salts of the N(R)₄ ⁺type in which radicals R, which may be identical or different, representa hydrogen atom or a linear or non linear, saturated or unsaturatedC₁-C₆ hydrocarbon radical that may be substituted by a hydroxyl group;or sulphonium salts; said salts being present alone or in a combination.

Ammonium salts that can in particular be cited include secondary orprimary amines such as isopropylamine, dimethylamine, diamines such asethylenediamine, or alkanolamines such as monoethanolamine.Trimethylsulphonium is a perfectly suitable sulphonium salt.

Preferred glyphosate derivatives for herbicidal application that can becited are isopropylamine, the monoethanolamine salt and thetrimethylsulphonium salt.

Advantageously, the herbicide content of the aqueous formulations of theinvention is in the range 80 to 510 g/l expressed in acid herbicideequivalents.

In accordance with one essential feature of the invention, the aqueousformulations comprises at least one principal surfactant selected fromalkylbetaines and alkyl(amidoalkyl)betaines.

Preferably, the principal surfactant corresponds to one or more of thefollowing formulae:

in which formulae:

R¹ represents a linear or branched alkyl group containing 3 to 30 carbonatoms, preferably 3 to 20 carbon atoms, such as propyl, dodecyl,hexadecyl, tetrahexadecyl, octyl, or mixtures thereof, or an alkamidegroup, such as dodecanamide;

R², which may or may not be identical, represent an alkyl radical,preferably a methyl radical;

R³ represents a hydrogen atom or a —CH₂COOM radical or an alkyl radical;

M represents an alkali metal, preferably sodium.

Said compounds, which can be used in the invention as principalsurfactants, are commercially available products and are sold by RhodiaChimie under the trade names Mirataine® and Wettem®. Advantageously,said commercially available products can be used as they are, withoutundergoing an initial treatment to reduce the amount of salt, forexample (sodium chloride in particular).

The amount of principal surfactant in the phytopathological formulationof the invention is advantageously in the range 20 to 180 g/l.

In addition to the principal surfactant, the phytopathologicalformulations of the invention comprise at least one additive selectedfrom at least one of the following compounds:

-   -   (i) amines or etheramines comprising at least one hydrocarbon        radical containing 2 to 24 carbon atoms, optionally        polyalkoxylated;    -   (ii) acid or non acid mono- and di-ester phosphates, optionally        polyalkoxylated;    -   (iii) alkali metal, alkaline-earth metal, ammonium,        alkylammonium, alkanolammonium, iron, zinc or manganese salts of        a mineral acid; and    -   (iv) alkylmonoglycosides or alkylpolyglycosides.

In accordance with a first possibility, compounds (i) are moreparticularly selected from amines comprising at least one linear orbranched, saturated or unsaturated radical containing 2 to 24 carbonatoms, preferably 8 to 18 carbon atoms, optionally comprising 2 to 30oxyalkylene motifs, preferably oxyethylene, or a mixture of a pluralitythereof.

In accordance with a second possibility, compounds (i) are selected frometheramines comprising at least one linear or branched, saturated orunsaturated radical containing 6 to 24 carbon atoms, preferably 8 to 20carbon atoms, optionally comprising 2 to 30 oxyalkylene motifs,preferably oxyethylene, or a mixture of a plurality thereof. Moreparticularly, the etheramines correspond to the following formula:

in which formula R represents a linear or branched, saturated orunsaturated hydrocarbon radical containing 6 to 24 carbon atoms,preferably 8 to 20 carbon atoms; OA, which may or may not be identicalfrom one motif to another and from one branch to another, represent anoxyethylene motif, preferably oxypropylene; and n, n′, which may or maynot be identical, represent a mean number in the range 1 to 30.

Examples of such amines that can be cited are amines derived from copraand containing 5 oxyethylene (OE) motifs, oleic amines containing 5 OE,amines derived from tallow containing 10 OE, etheramines correspondingto the above formula, in which radical R is an alkyl radical containing12 to 15 carbon atoms, the number of OE motifs being in the range 20 to30.

It should be noted that highly advantageously, the amount of compounds(i) represents 0 to 120 g/l of the formulation. In a particularimplementation of the invention, the amount of this type of compound isin the range 0 to 60 g/l. Preferably, the phytopathological formulationsare free of them.

Turning now to compounds (ii), these are preferably selected from acidor non acid phosphate mono- or di-esters, optionally polyalkoxylated,with formula (V) below:(AO)_(3-m)P(═O)(OM)_(m)  (V)in which:

-   -   A, which may or may not be identical, represent a group        R′¹—O(CH₂—CHR′²—O)_(n) in which:        -   R′¹, which may or may not be identical, represent a linear            or non linear, saturated or unsaturated C₆-C₂₀ hydrocarbon            radical, preferably C₈-C₁₈;        -   R′², which may or may not be identical, represent a hydrogen            atom or a methyl or ethyl radical, preferably a hydrogen            atom;        -   n is a mean number of motifs in the range 0 to 10,            preferably in the range 2 to 10;

M, which may or may not be identical, represent a hydrogen atom, analkali or alkaline-earth metal, a N(R³)₄ ⁺ type radical in whichradicals R³, which may or may not be identical, represent a hydrogenatom or a linear or non linear, saturated or unsaturated C₁-C₆hydrocarbon radical optionally substituted with a hydroxyl group;

m is a whole number in the range 1 to 2.

It should be noted that compound (ii) can be in the form of a monoester,a diester, or a mixture of these two esters.

Further, the amount of compound (ii), if present in the formulation ofthe invention, is in the range 0 to 120 g/l.

Compound (iii) is advantageously selected from alkali metal oralkaline-earth metal, ammonium, or linear or non linear, saturated orunsaturated C₁-C₆ alkylammonium or alkanolammonium sulphates, nitratesor phosphates; or from iron, zinc or manganese sulphates, used alone oras a mixture.

The amount of compound (iii) in the formulations, if present, is moreparticularly in the range 0 to 200 g/l.

Compound (iv) is advantageously octylglycoside, an octylpolyclycoside,decylglycoside, a decylpolyglycoside, or a mixture thereof.

The amount of compound (iii) in the formulations, if present, is moreparticularly of from 0 to 150 g/l.

In accordance with a preferred characteristic of the invention, theproportion by weight of principal surfactant/sum of additives (i) to(iv) is in the range 6/1 to 1/2.

Further, in one implementation of the invention, the total amount ofprincipal surfactant and additive(s) represents 60 to 180 g/l of theformulation.

The formulations can also comprise additives that are conventional inthe field such as anti-foaming agents, for example organopolysiloxanes;or thickening agents such as xanthan gum type polysaccharides,alginates, carboxylated or hydroxylated methylcelluloses, syntheticmacromolecules of the polyacrylate, polymaleate, polyvinylpyrrolidone,polyethylene glycol or polyvinyl alcohol type, or of the inorganic typesuch as bentonites.

The formulation can also comprise auxiliary additives such asantioxidants, anti-UV agents, colorants, etc. It may also comprise afurther solvent such as an alcohol, for example isopropanol, typicallyup to 15% by weight.

The amount of these additives listed above is normally less than 10% byweight, preferably 1% by weight or less, advantageously 0.1% by weightor less compared with the composition weight.

The compositions of the invention can be prepared by mixing theirdifferent constituents with moderate stirring.

This operation preferably takes place at a temperature in the range 15°C. to 60° C., preferably at a temperature close to ambient temperature(15-30° C.).

Usually, the principal surfactant is preferably only added once theother constituents have been mixed.

The phytopathological formulations of the invention are thus used totreat plants, normally after diluting with water.

Non-limiting examples of the invention will now be described.

EXAMPLE 1

A mixture with the following composition was prepared in water (up to 1liter):

*glyophosate isopropylamine salt (46% acid) 783 g/L *Mirataine ® D40(*)80 g/L (as the solid content) *Geronol ® CF/AR (**) 20 g/L *oleic aminecontaining 5 OE motifs 20 g/L (*)Mirataine ® D40 (sold by Rhodia):Aqueous composition comprising water and an alkyldimthyldimethylbetaine,wherein the alkyl is a mixture of about 70 weight % lauryl (C₁₂, lautyl)and 30 weight % tetradecyl (C₁₄), the composition having a solid contentof the alkyldimthyldimethylbetaine of 40 weight %. (**)Geronol ® CF/AR(sold by Rhodia Geronazzo) is a mixture of mono- and di-ester phosphateswith formula (I) from saturated C₄-C₁₀ aliphatic alcohols and comprisinga mean of 3 to 8 motifs of ethylene oxide, and M is isopropyl ammonium.

A composition was obtained the efficacy of which was equivalent to acomposition comprising the same amount of glyphosate (expressed as theacid equivalent) and with a concentration of 180 g/l of ethoxylatedoleic amine (15 motifs).

The formulation was stable on storage at ambient temperature and at 54°C.

EXAMPLE 2

A mixture with the following composition was prepared in water:

*glyophosate isopropylamine salt (46% acid) 783 g/l *Mirataine ® D40(*)103 g/l (as the solid content) *ammonium sulphate 17 g/l

A composition was obtained the efficacy of which was equivalent to acomposition comprising the same amount of glyphosate (expressed as theacid equivalent) and with a concentration of 180 g/l of ethoxylatedoleic amine (15 motifs).

The formulation was stable on storage at ambient temperature and at 54°C.

1. An aqueous phytopathological formulation comprising: a hydrosolublesalt of an N-phosphonomethyl glycine herbicide; at least one principalsurfactant comprising a C₁₂-C₁₄ alkylbetaine or a mixture thereof; andat least one additive comprising a C₈-C₁₀ alkylpolyglycoside or amixture thereof.
 2. The formulation of claim 1, wherein the amount ofherbicide ranges between 80 and 510 g/L, expressed in acid herbicideequivalents.
 3. The formulation of claim 1, wherein the principalsurfactant is present in an amount ranging from 20 and 180 g/L.
 4. Theformulation of claim 1, wherein the additive comprises anoctylpolyclycoside, a decylpolyglycoside, or a mixture thereof.
 5. Theformulation of claim 1, wherein the additive is present in an amountranging from 0 and 150 g/L.
 6. The formulation of claim 1, wherein theproportion by weight of principal surfactant to additive ranges frombetween 6/1 to 1/2.
 7. The formulation of claim 1, wherein the principalsurfactant and the additive comprise a total amount ranging from 60 to180 g/L of the formulation.
 8. The formulation of claim 1, wherein theamount of additive is less than 10% by weight of the formulation.
 9. Theformulation of claim 8, wherein the amount of additive is 1% or less byweight of the formulation.
 10. The formulation of claim 9, wherein theamount of additive is 0.1% or less by weight of the formulation.
 11. Theformulation of claim 1, wherein the amount of additive ranges from 0.1%to less than 10% by weight of the formulation.
 12. An aqueousphytopathological formulation comprising: a hydrosoluble herbicide saltof N-phosphonomethyl glycine with an alkali metal, a secondary orprimary amine, a diamine, an alkanolamine, or a sulfonium; at least oneprincipal surfactant comprising a C₁₂-C₁₄ alkylbetaine or a mixturethereof; and at least one additive comprising a C₈-C₁₀alkylpolyglycoside or a mixture thereof.
 13. An aqueousphytopathological formulation comprising: an isopropyl amine salt of anN-phosphonomethyl glycine herbicide; at least one principal surfactantcomprising a C₁₂-C₁₄ alkyldimethylbetaine, and at least one additivecomprising a C₈-C₁₀ alkylpolyglycoside.